Treatment of hydrocarbons



22, 1942. a. M'.'MARKS TREATMENT or! BYDROGARBONS- Fi'ied Sept. 27, 1941 Invent-of V Ernest M. Marks B 1 /M 45%!- Attorney water content of the aluminum oxide components Patented Dec.22,1 9 l2 UNITED STATES 'PATE NT OFFICE.

F HYDROCARBONS Ernest M. Marks, Lansdowne, Pa., assignor to The Atlantic Refining Company, Philadelphia,

Vania Pa, a corporation of Pennsyl Application September 27, 1941', Serial No. 412,541

7 Claims. (01. 196-52) a converted in accordance with this invention.

It is a further object of this invention to improve the antiknock qualities of gasoline or naphtha distillate and to increase the lead susceptibility thereof by subjecting such distillates to re- 1 forming conditions of temperature and pressure in the presence of a catalyst. Such reforming operation involves essentially a dehydrogenation and structural rearrangement of the'dist te molecules, with or withoutcracking and c ge in boiling range or volatility of the reformed distillate.

It -isa further objectofthis invention to eiiect conversion of hydrocarbons in the presence of a catalyst comprising aluminum oxide and an alkali metal borate, such catalyst containing limited amounts of water, preferably from about 5 per cent to about 15 per cent by weight.

It is a further object of this invention to effect conversion of hydrocarbons in the presence of a catalyst comprising aluminum oxide and an alkali metal borate, the moisture content of the hydrocarbons being controlled to provide .a'. charging stock containing not more than about 40 parts per million (0.004 per cent by weight) of water.

I have found that the most effective conversion oxide and an alkali metal borate, and containing from about 5 per cent to about per cent by weight of water in chemical combination. Inthe conversion of high boiling oils, such as gas oil, into gasoline, temperatures of. the order of from about 850 F..to 1050 F. and pressures up to about 3000 pounds per square inch may be employed, while in the reforming of gasoline or naphtha distillatesfor the improvement of the antiknock quality thereof, temperatures of the order of 975 F. to 1100 F. and pressures of the order of from atmospheric to about 1500 pounds per square inch 7 may be advantageously utilized. The reaction time or space velocity may be varied, depending upon the temperature-pressure conditions and the results desired. In general the contact time may be somewhat longer in the conversion of high'boiling oils into lower boiling hydrocarbons such as gasoline, than in the reforming of gasoline or I naphtha distillates for the improvement in antiknock quality thereof. For example, in cracking high boiling oils, the space velocity may beof the order of 1 volume of charge oil per volume of catalyst per hour, whereas in the reforming of distillates, the spacevelocitymay be of the order of 1.5 to 4 volumes of charge oil per volume of catalyst per hour.

v The catalyst to be employed in accordance with this invention comprises aluminum oxide .or bauxite which has been impregnated with an alkali metal borate, said aluminum oxide or bauxite containing from about 5 per cent to about 15 per cent by weight of water, most of which is chemically combined. The water, content or volatile matter is found by heating the oxide or bauxite at 1800 F. for 20 minutes, and determinof hydrocarbons may be obtained when the water content (volatile matter) of the aluminum oxidealkali metal borate catalyst, and particularly the thereof, is maintained within the ran e of from about 5 per cent to about 15 per cent by weight, and the ,waten content of the hydrocarbons charged is maintained at not more than about 40 parts per million. Substantial deviation of the water contents of either the catalyst or the hydroing the loss in weight. Such catalyst maybe prepared by soaking granular aluminum oxide of proper water content with an aqueous solution or suspension of an alkali metal borate, and thereafter drying the impregnated granular material by heating at temperatures notin excess of about 1000 F. 0r, alternatively,- finely divided alumi-.' num oxide may be impregnated with an alkali metal borate solution or suspension, and the moist material thereafter granulated or formed intosuitable pellets or masses. The quantity of borate to be employed may vary from about 0.1 per cent reaction, such catalyst comprising aluminum to 10 per cent or more by weight of the aluminum oxide, quantities of the order of from about 1 per cent to about 5 percent being preferred. Among the borates which may be utilized are the metaborates. tetraborates, pentaborates. hexaborates, octaborates and dodecaborates of sodium, .potas-- sium and lithium.

I .tmduced by means of pipe The water content of the hydrocarbon oil to be converted may be'controlled by dehydrating the all, if the water content is' substantially in excess of about 40 parts per million. Oils containin I substantially no water, or water in amounts up to about 40 parts per million, are satisfactory. Those containing water in excess of about 40 parts per million are not susceptible of high conversion yields. when necessary, dehydration of the oil to the proper water content may be accomplished by air blowing, or treatment with dehydrating adsorbents or chemical agents commercially avail- .able for dehydrating purposes.

My invention may be further illustrated with reference to the accompanying drawing, which shows diagrammatically a system suitable for carrying out my process.

Hydrocarbon oil, suc water content of not more than 40 parts per million, is supplied from a source (not shown) through valve-controlled pipe I and is passed by means of pipe 2 to heat exchanger 3, wherein the oil is preheated by indirect heat exchange with cracked products from the catalytic chamber hereinafter described. The preheated oil is passed from heat exchanger 3 through pipe 4 to pump 5, from which it is delivered to the tubular heating coil v6 wherein the temperature of the oil is raised to about 950 F., under a pressure of from about 25 to about 50 pounds perv square inch. Higher pressures, ofcourse, may be used. In the coil 6 the oil is vaporized and the heated vapors are passed therefrom by means of pipe 1 into the upper section of catalyst chamber 8 containing a granular catalyst 9 comprising A120: impregnated, for example, with 1 per cent by weight of sodium borate (NarBio'l) and containing from about per cent to about l5,per centby weight of water. In the chamber 8 cracking of the heated oil in contact with the catalyst takes place, with the production of hydrocarbon gases, Ha, cracked gasoline and gas oil, and small "as gas oil having a amounts of tar. The cracked products, at a temperature of the order of 950 F., are with- 'drawn from the lower section of chamber 8 and are passed by means of pipe l0 through heat exchanger 3 in indirect heat exchange with relatively cool charge oil introduced through valvecontrolled pipe i and pipe 3 the hot, cracked products are partially cooled, and thence delivered by valve-controlled pipe H to fractionating'column l,2 provided with contasting plates or trays -l3 heating coil l4 and cooling or reflux coil II. The cracked products are fractionated in column I2 to produce an overhead fraction comprising cracked. gasoline and gases, comprising cracked gas oil and small amounts 9f tar. The cracked gas oil and tar may be withdrawn fromthe bottom of column l2 by means of vnlve-controlled 'tion thereof may oil, to the tubular heating coil 6. oi' the cracked gas'oil'and tar may from the system through valve-controlled and disposed ofas desired;

be recycled, with fresh charge Theremainder be withdrawn pipe H 2. In the exchanger I and a bottoms fraction or residuepipe and, minds por- I column and passed by means of valve controlled pipe 23 to storage (not shown). If desired, a

'means of valve-controlled pipe 25. If desired,

at least a portion of the uncondensed gas or C1-C4 hydrocarbons. may be recycled to the tubular heating coil 6 by. means of valve-controlled pipe 26, compressor 21 and .pipe 28.

' In the operation of the catalyst chamber 8, the activity of the catalyst may be maintained or increased by the introduction of gases such as steam, oxygen, or carbon dioxide, or mixtures thereof, by means of valve-controlled pipe 29. And at such time as the granular catalyst 9 becomes fouled with carbon or tarry matter, the conversion system may be shut down and the catalyst regenerated by contacting with air -or steam at elevatedtemperatures, preferably not in excess of about 1000 F. Such revivifying agents may be introduced into chamber 8 through valve-controlled pipe 29 and may be withdrawn therefrom, together with the matter contaminating the catalyst, by means of valvecon trolled pipe 30.

The reforming of gasoline or naphtha distillatesfor the improvement-pf antiknock quality' may be carried out in a r'na'nner similar to that above described inconnection with gas oil cracking. In the reforming operation, it is advantageous to employ somewhat higher temperatures,

pressures, and rate of flow than are utilizedin the conversion. of high boiling oils such as gas oil. Depending upon the'nature of the distillate to be reformed, the operating conditionsmay be varied in order to accomplish reforming with a controlled amount of, cracking, or with substantially no cracking, as may be .desired.

My process may be further illustrated by the following examples, which, however, are not in tended as limiting the scopetherecf.

The results given in table were obtained by cracking, in a single pass at atmospheric pressure, a petroleum gas oil under the conditions and with the catalysts substantially as set forth,

The gas oil employed had an A. P. I. gravity of 3l.4,- and a boiling range of 256 F. to 741 F.

The borate-containing catalysts were prepared by impregnating granular $4; mesh A120: with aqueous solutions of sodium borate and drying The gasoline vapors and are passed from.

intthe'latterjs stabilized to obtain th desired boiling I range 'and" oiinc may be withdrawn from the bottom 0 olatility. The stabilized gasto 400 F.iend point.

I nditions Home Gasoil V list) I I Contact Weight ER d8 g ffi pe cent socon 8mm l 3lP.P.M GranularAlaOr+ 1002 NlIBIOI (9.5 I I 64 113 :12 P M om iiu afi ofi' ioor I I :IB|01.(9.)59 M .3 68'P.P.-M. Granular-A110: 5

Nnno i- 1002 so 20.0 19.8 312 P M Gratinafia s v I I v Nnmq fg; 1. 0 31.4 10.1. "svrrM' c'fifiiti? O ran a I NlrBcOr (1.6 o an) minAlaQs).

i the impregnated granules. The gasoline was cut yielis of e.

Fromtheaboveitwfilbesecnthatthe Ahoa-Ramiow at least 5 percent by-ofwater,andgascflsccntainingnotmorethanahcutwmrtspermillion (REEL) ciwaterpmducethehigher 'betweenfipercentandfipercentbyweight of water. i

2. A prccms for the conversion of a hydrocarhon stock con not more than about 40 parts per of water into other hydrocarhens, which comprises mniaciing said stock with a. catalyst comprising i s m oxide and an alkali metal horate at. a smiiiciemziy elevated temperature to efieci said conversion.

3. A process for the conversion of a hydrocarhon stock containing not more than about 4Q parts per million of water inio other hydrocarhens, which comprises contacfing saiii stock with a caialyst comprising aimmnumoxide and, an alkali metal horate at a smciently eievate temperature to effect said conversion, said caca- Iystcontainingbetween5percemand isper cent by weight of water.

4. A process for the conversion of high hydrocarbon oil into lower boiling ydrocarbons, which comprises subjecting a high boiling oil containingnotmorethanahoutwpartsper of water to cracking itmes m theotacataiystcomprlslngoxideandanalkaiimetalbomtesaid betweeniipercentandlfi'pcrcm bywelghtofwater'.

5. A places for the conversion of bonscontalningnot moxethanaboucmmris pcrmlllionofwaterintogasoiinehaimproved qualities, which. comprises said to a tem within the range of from about 950 Rio IIISWRJnQheceofacaiaWst mgalnminumoxidesmianmeiai andcontaining5percentsmii5per centbwweight ofwatenandmgihe conversion products a on '1 1 s i- "1' i am range.

6. A process for the conversion of haybonsoontainingnotmoreabwcwmmm ct-waterinio 1': Hamil qualities, which comzmses h hydmcarbomto atemperamewithinfihex or fmm ahout 956 F. to about i656 F, supemeric pressure, in the presence of a M, t: r prising vac-m1 oxide m an metal hon-ate, and confisining h 5 per cent I from the comveision modem 52, me-

,wi. the mime boiling iion I. A mm: the cmveisicn 02E Imyfimccarnetmorethamaimmsiiwfis perof.

water into e havm fi m.

qualities, which cc heah'ng mid hydro so a wrewithinthemngeoifmmahoutgiwfitoamfi 1650 F. mder We, in theofacataiysccompflsing: oxideandsodiomborataamiccmheflw 5percenfiandl5percentbyweigmfiofiwm, 1 fromthe conversion pmzmcisa and l5percentiiyweight cfwamemami 

